Process for the preparation of lightly-branched hydrophobes and the corresponding surfactants and applications thereof

ABSTRACT

Processes to prepare lightly branched surfactant products comprise combining at least one olefin and a coordination-insertion catalyst under conditions such that at least one oligomer product is formed. The surfactant products comprise a main carbon chain containing an average of between 0.5 and 2.5 branches, wherein more than 50% of the branches are ethyl branches, wherein the branches are located more than one carbon away from each end of the main carbon chain in more than 20% of surfactant product molecules.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to International Patent Application No.PCT/US2014/042887, filed Jun. 18, 2014, which claims priority to U.S.Provisional Application No. 61/840,765, filed Jun. 28, 2013, all ofwhich are hereby incorporated herein by reference in their entireties.

FIELD

The invention relates to processes for the manufacture oflightly-branched hydrophobes, and their corresponding nonionic andanionic surfactants.

BACKGROUND

Surfactant molecules generally comprise a water-soluble moiety(hydrophile) and an oil-soluble moiety (hydrophobe). Various hydrophilicgroups, such as polyoxyethylene, polysaccharide, quaternary ammonium,amine oxide, sulfate, sulfonate, sulfosuccinate, carboxylic, and thelike, are attached to an alkyl, alkenyl, or alkaryl hydrophobe thatusually contains 8 to 20 carbon atoms through different linkagechemistries. The hydrophobe structure affects the properties,performance, biodegradability, toxicity, and therefore the applicationof the surfactants. Hydrophobes may be derived from natural oils andfats, which are typically linear. Linear hydrophobes are favorable inaffording ready biodegradability of surfactants. However, they arelimited in providing key performance features of surfactants, such ashigh solubility, easy handling and good wetting.

Hydrophobes can also be synthesized from petrochemical or coal-derivedraw materials. Synthetic hydrophobes include the linear versions thatare functionally equivalent to the linear hydrophobes derived fromnatural oils and fats. One advantage of synthetic hydrophobes is theflexibility of creating various branching structures by using differentchemistries and processes. In general, branched hydrophobes help affordsurfactants with better handling properties, less stable foam, andenhanced wettability, which are highly desirable features in manyapplications. The highly branched structure of the hydrophobe howevermay cause poor surfactant biodegradability. It is believed that alightly branched hydrophobe may provide a favorable balance between highperformance and ready biodegradability for the corresponding surfactant.

Current processes for generating lightly branched surfactants requiremultiple steps to obtain the desired branching. In addition, suchprocesses typically require the use of more than one starting monomer.Thus, there is a need for a process for preparing surfactants with thesame ability to reduce surface tension as the surfactants produced bythe current processes, but in fewer steps. Furthermore, there is a needfor a process for preparing surfactants from only one starting monomer.

BRIEF SUMMARY

In one aspect, a process is provided comprising combining at least oneolefin and at least one coordination-insertion catalyst and, optionally,an alpha-olefin, wherein the coordination-insertion catalyst is ametal-ligand complex wherein the metal is selected from zirconium,hafnium and titanium, and has an ethylene/octene reactivity ratio up to20 at an operating reactor temperature, and a kinetic chain length up to20 monomer units; under conditions such that at least one oligomerproduct is formed. The oligomer product includes a main carbon chaincontaining an average of between 0.5 and 2.5 branches, wherein more than50% of the branches are ethyl branches, wherein the branches are locatedon average more than one carbon away from each end of the main carbonchain in more than 20% of oligomer product molecules, wherein thebranches are situated at a second carbon relative to an unsaturated endof the main carbon chain in less than 40% of the oligomer productmolecules, and wherein the oligomer product contains greater than 50%vinyl olefin. The process further comprises fractionating the oligomerproduct to produce a fractionated oligomer product, such that theaverage carbon number of the fractionated oligomer product is between 8and 28; and hydroformylating the fractionated oligomer product toproduce an aldehyde product or sulfonating the fractionated oligomerproduct to produce a sulfonated surfactant product.

In another aspect, a process comprises combining at least one olefin andat least one coordination-insertion catalyst and, optionally, analpha-olefin, wherein the coordination-insertion catalyst is ametal-ligand complex wherein the metal is selected from zirconium,hafnium and titanium, and has an ethylene/octene reactivity ratio up to20 at an operating reactor temperature, and a kinetic chain length up to20 monomer units; under conditions such that at least one oligomerproduct is formed. The oligomer product includes a main carbon chaincontaining an average of between 0.5 and 2.5 branches, wherein more than50% of the branches are ethyl branches, wherein the branches are locatedon average more than one carbon away from each end of the main carbonchain in more than 20% of oligomer product molecules, wherein thebranches are situated at a second carbon relative to an unsaturated endof the main carbon chain in less than 40% of the oligomer productmolecules, and wherein the oligomer product contains greater than 50%vinyl olefin. The process further comprises fractionating the oligomerproduct to produce a fractionated oligomer product, such that theaverage carbon number of the fractionated oligomer product is between 8and 28; hydroformylating the fractionated oligomer product to produce analdehyde product; and hydrogenating the aldehyde product to produce analcohol product.

In another aspect, an alcohol product is provided, comprising a maincarbon chain containing an average of between 0.5 and 2.5 branches,wherein more than 50% of the branches are ethyl branches, wherein thebranches are located more than one carbon away from each end of the maincarbon chain in more than 20% of alcohol product molecules.

In yet another aspect, a lightly branched surfactant product isprovided, comprising a main carbon chain containing an average ofbetween 0.5 and 2.5 branches, wherein more than 50% of the branches areethyl branches, wherein the branches are located more than one carbonaway from each end of the main carbon chain in more than 20% ofsurfactant product molecules.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a formula drawing of a coordination-insertion catalyst of theformula2′,2′″-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol)-zirconiumdimethyl.

FIG. 2 is a formula drawing of a coordination-insertion catalyst of theformula3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-2′-(2-((3′-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-fluoro-2′-hydroxy-5′-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-yl)oxy)ethoxy)-3′,5′-difluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol-zirconiumdimethyl.

FIG. 3 is a formula drawing of a coordination-insertion catalyst of theformula3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-2′-(2-((3′-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,5-difluoro-2′-hydroxy-5′-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-yl)oxy)ethoxy)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol-zirconiumdimethyl.

FIG. 4 is a formula drawing of a coordination-insertion catalyst of theformula2′,2′″-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′,5′-difluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol)-hafniumdimethyl.

FIG. 5 is a formula drawing of a coordination-insertion catalyst of theformula2′,2′″-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol)-hafniumdimethyl.

FIG. 6 is a formula drawing of a coordination-insertion catalyst of theformula6′,6′″-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol)-hafniumdimethyl.

FIG. 7 is a formula drawing of a coordination-insertion catalyst of theformula2′,2′″-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′,5′-difluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol)-zirconiumdiemethyl.

FIG. 8 is formula drawing of an organophosphorus ligand,tris(2,4-di-tert-butylphenyl)phosphite (L).

FIG. 9 is a reaction scheme for the preparation of2-(2-bromoethoxy)-1,5-difluoro-3-iodobenzene.

FIG. 10 is a reaction scheme for the preparation of2-(2-(2,4-difluoro-6-iodophenoxy)ethoxy)-5-fluoro-1-iodo-3-methylbenzene.

FIG. 11 is a reaction scheme for the preparation of3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-2′-(2-((3′-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,5-difluoro-2′-hydroxy-5′-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-yl)oxy)ethoxy)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol.

FIG. 12 is a reaction scheme for the preparation of(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-2′-(2-((3′-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,5-difluoro-2′-hydroxy-5′-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-yl)oxy)ethoxy)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol)dimethyl-zirconium.

DETAILED DESCRIPTION

This invention provides a new process to produce lightly mid-branchedolefins and alcohols as hydrophobes for surfactants, in which majorityof the mid-branched groups is ethyl or higher alkyl, at least 50% of thebranches are ethyl or higher alkyl, and there is no (<1%) terminalisopropyl type of branch.

The present process is advantageous in that it generates lightlybranched surfactants for improved performance while maintaining readybiodegradability. Furthermore, the process provides significant costadvantage since (1) it generates the desired branching structure in onestep to the oligomer, without further processing, and (2) can beprepared from only one monomer, such as ethylene.

The process comprises several steps: (1) formation of a lightly branchedethylene oligomer, (2) formation of a hydrophobe (in some embodiments,the hydrophobe is the ethylene oligomer itself), and (3) formation of asurfactant product. The lightly branched hydrophobes may be preparedfirst via ethylene oligomerization, generating a mixture of lightlybranched olefins, which are then (1) converted to alcohols, then (2a)alkoxylated to generate nonionic surfactants, (2b) first ethoxylated oralkoxylated then sulfated to generate anionic ethoxysulfate oralkoxysulfate surfactants or (2c) sulfated to generate sulfatedsurfactants. The lightly branched hydrophobe may also comprise theoligomeric lightly branched olefin which is then (3) directly convertedto anionic sulfonated surfactants via sulfonation, respectively.

The preparation of the oligomer involves (1) oligomerization of theolefin using a catalyst and appropriate process conditions to makeoligomeric products that approximate a Schulz-Flory distribution ofoligomeric products, and (2) fractionation to obtain the desiredfraction to generate the hydrophobe or fractionated oligomer product,such that the average carbon number of the fraction is between C8 andC28. Preferably, the average carbon number of the fractionated oligomerproduct may be between C8 and C10, between C8 and C12, between C8 andC14, between C10 and C12, between C10 and C14, between C10 and C16,between C12 and C14, between C12 and C16, between C14 and C16, betweenC14 and C18, or between C16 and C18. When a carbon number is given, itmeans a distribution of molecules averaging that carbon number. Forexample C12 means a distribution of molecules averaging twelve carbonatoms.

The starting olefin may be ethylene alone, or a proportion of analpha-olefin comonomer may be included along with ethylene. The startingolefin may also be any terminal olefin, for example, linear olefins. Ifan alpha-olefin is to be included, it may be selected from, innon-limiting example, linear alpha-olefins having from 3 to 12 carbons,such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene, and combinations thereof.

The starting olefin mixture may contain three types of olefins: olefinswith vinyl groups, olefins with vinylidene groups, and olefins withvinylene groups. The olefin mixture may comprise greater than 50%olefins with vinyl groups, preferably between about 70% and 80% olefinswith vinyl groups. The olefin mixture may also comprise about 20%olefins with vinylidene groups and about 5% olefins with vinylenegroups. Preferably vinylidene group is 1,1-ethenediyl.

Notwithstanding the above, it is preferred that only a minor amount ofalpha-olefin is included, if any. That amount preferably ranges from 0to 30 mol %; more preferably from 0 to 25 mol %; still more preferablyfrom 0 to 20 mol %; yet more preferably from 0 to 10 mol %; and mostpreferably from 0 to 5 mol %. The amount of added alpha-olefin is mostcommonly preferred to be 0 mol % because added alpha-olefins tend to bemore costly than the spectrum of alpha-olefins that are created in-situ.While ethylene feed streams often have a small fraction (less than 1 mol%) of alpha-olefin monomer impurities such as propylene, it is expectedthat such would have no significant detrimental effect on processoperation or oligomer properties.

In the inventive process the selected starting olefin or olefins, is/arecontacted with a suitable coordination-insertion catalyst. As the termis used here, “coordination-insertion” means that the catalysts arecapable of consecutively inserting unsaturated monomers, with the resultthat previously unsaturated carbons in the monomers and the oligomerbecome the backbone of a new oligomer. This catalyst may be selected, inone embodiment, from a wide variety of metal-ligand complexes. Thoseskilled in the art will be aware that catalyst performance varies withprocess temperature and also may vary with reaction mixture compositionand conversion. Preferred catalysts are those exhibiting an activitylevel of 100,000 grams of oligomer per gram of catalyst metal (g/g cat).Also preferred are catalysts capable of producing a chain terminationrate that results in product oligomer of a desired molecular weight andhaving a high fraction, preferably at least 25%, more preferably atleast 50%, and most preferably at least 75%, of vinyl groups.

Kinetic chain length is also important in identifying particularlysuitable catalysts for the present invention. Kinetic chain length isdefined as the average number of monomeric repeat units incorporated bya catalyst before a chain transfer or chain growth terminating reaction.

Examples of suitable coordination-insertion catalysts may generallyinclude, in certain non-limiting embodiments, metal-ligand complexesincluding any of the metals zirconium, hafnium, or titanium, andpreferably zirconium or hafnium. Among these catalysts may be certainmetallocene catalysts, including certain constrained geometry catalysts,and bis-phenylphenoxy catalysts, provided that the selected catalystmeets the ethylene/octene reactivity ratio and kinetic chain lengthrequirements as defined hereinabove.

The metallocene compounds useful herein are cyclopentadienyl derivativesof titanium, zirconium, and hafnium. These metallocenes (e.g.,titanocenes, zirconocenes and hafnocenes) may be represented by thefollowing formula:

wherein M is the metal center, and is a Group 4 metal, preferablytitanium, zirconium or hafnium;

T is an optional bridging group which, if present, in preferredembodiments is selected from dialkylsilyl, diarylsilyl, dialkylmethyl,ethylenyl (—CH₂—CH₂—) or hydrocarbylethylenyl wherein one, two, three orfour of the hydrogen atoms in ethylenyl are substituted by hydrocarbyl,where hydrocarbyl can be independently C₁ to C₁₆ alkyl or phenyl, tolyl,xylyl and the like, and when T is present, the catalyst represented canbe in a racemic or a meso form;

L₁ and L₂ are the same or different cyclopentadienyl, indenyl,tetrahydroindenyl or fluorenyl rings, optionally substituted, that areeach bonded to M, or L₁ and L₂ are the same or differentcyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, which areoptionally substituted, in which any two adjacent R groups on theserings are optionally joined to form a substituted or unsubstituted,saturated, partially unsaturated, or aromatic cyclic or polycyclicsubstituent;

Z is nitrogen, oxygen or phosphorus;

R′ is a cyclic linear or branched C₁ to C₄₀ alkyl or substituted alkylgroup; and

X₁ and X₂ are, independently, hydrogen, halogen, hydride radicals,hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbylradicals, substituted halocarbyl radicals, silylcarbyl radicals,substituted silylcarbyl radicals, germylcarbyl radicals, or substitutedgermylcarbyl radicals; or both X are joined and bound to the metal atomto form a metallacycle ring containing from about 3 to about 20 carbonatoms; or both together can be an olefin, diolefin or aryne ligand.

Among the metallocene compounds which can be used in this invention arestereorigid, chiral or asymmetric, bridged or non-bridged, or so-called“constrained geometry” metallocenes. See, for example and methods forpreparation, U.S. Pat. No. 4,892,851; U.S. Pat. No. 5,017,714; U.S. Pat.No. 5,132,281; U.S. Pat. No. 5,155,080; U.S. Pat. No. 5,296,434; U.S.Pat. No. 5,278,264; U.S. Pat. No. 5,318,935; U.S. Pat. No. 5,969,070;U.S. Pat. No. 6,376,409; U.S. Pat. No. 6,380,120; U.S. Pat. No.6,376,412; WO-A-(PCT/US92/10066); WO 99/07788; WO-A-93/19103; WO01/48034; EP-A2-0 577 581; EP-A1-0 578 838; WO 99/29743, and also theacademic literature, e.g., “The Influence of Aromatic Substituents onthe Polymerization Behavior of Bridged Zirconocene Catalysts,” Spaleck,W., et al., Organometallics 1994, Vol. 13, pp. 954-963;“ansa-Zirconocene Polymerization Catalysts with Annelated RingLigands—Effects on Catalytic Activity and Polymer Chain Lengths,”Brintzinger, H., et al., Organometallics 1994, Vol. 13, pp. 964-970;“Constrained geometry complexes—Synthesis and applications,”Braunschweig, H., et al., Coordination Chemistry Reviews 2006, 250,2691-2720; and documents referred to therein.

The process uses as catalysts a particular subset of thebis-phenylphenoxy compounds described in US20110282018. These are termedmetal-ligand complex catalysts that combine a transition metal centerand any of a wide variety of bis-phenylphenoxy-containing ligandsconforming to formula (III), provided that the following limitations aremet. First, the bridge, L, between the Z moieties is from 2 atoms to 8atoms in length. Second, the Z moieties may be selected independentlyfrom oxygen, sulfur, phosphorus(C₁₋₄₀)hydrocarbylene, andnitrogen(C₁₋₄₀)hydrocarbylene. Third, the ligand has a halogen atomlocated in at least one of the positions on the benzene rings in theR^(1a) and/or R^(1b) position of formula (III), i.e., at a position, orpositions, that is/are ortho to the bridged Z moieties. The term“halogen atom” means a fluorine atom radical (F), chlorine atom radical(Cl), bromine atom radical (Br), or iodine atom radical (I). Preferablyeach halogen atom independently is a Br, F, or Cl radical, and morepreferably a F or Cl radical. Fourth, the metal M is preferably selectedfrom zirconium (Zr), hafnium (Hf), and titanium (Ti), and morepreferably is either Zr or Hf.

The members of the catalyst family defined are generally convenient toprepare and may operate efficiently and over a wide thermal operatingrange, in some non-limiting embodiments withstanding temperaturesexceeding 200° C. Such catalysts may, themselves, be of effectively anymolecular weight (M_(w)), but in certain non-limiting embodimentspreferably range from 200 Daltons (Da) to 5,000 Da. Preparation mayinclude, in non-limiting embodiments, construction of a suitable ligandstructure followed by its reaction with a salt of the desired transitionmetal, which effects the desired metal-ligand complexation. Additionaland highly detailed preparation information may be found in, e.g., thepreviously referenced US20110282018; US Serial NumberPCT/US2012/0667700, filed Nov. 28, 2012, claiming priority to U.S.Provisional Application 61/581,418, filed Dec. 29, 2011; and U.S. Ser.No. 13/105,018, filed May 11, 2011, Publication Number 20110282018,claiming priority to U.S. Provisional Application 61/487,627, filed Mar.25, 2011. Those skilled in the art will recognize that similar andanalogous processes may be used to prepare other usefulbis-phenylphenoxy compounds falling within the given general definition.

In certain embodiments, such suitable catalysts may generally include,in more specific but non-limiting embodiments, metal-ligand complexes offormula (III)

wherein M is titanium, zirconium, or hafnium, each independently beingin a formal oxidation state of +2, +3, or +4; n is an integer of from 0to 3, wherein when n is 0, X is absent; each X independently is amonodentate ligand that is neutral, monoanionic, or dianionic, or two Xare taken together to form a bidentate ligand that is neutral,monoanionic, or dianionic; X and n are selected such that themetal-ligand complex is, overall, neutral; each Z is independently O, S,N(C₁-C₄₀)hydrocarbyl, or P(C₁-C₄₀)hydrocarbyl; L is(C₁-C₄₀)hydrocarbylene or (C₁-C₄₀)heterohydrocarbylene, wherein the(C₁-C₄₀)hydrocarbylene has a portion that comprises a 2- to 8-atomlinker backbone linking the Z moieties and the(C₁-C₄₀)heterohydrocarbylene has a portion that comprises a 2- to 8-atomlinker backbone linking the Z moieties, wherein each atom of the 2- to8-atom linker of the (C₁-C₄₀)heterohydrocarbylene independently is acarbon atom or a heteroatom, wherein each heteroatom independently is O,S, S(O), S(O)₂, Si(R^(C))₂, Ge(R^(C))₂, P(R^(P)), or N(R^(N)), whereinindependently each R^(C) is unsubstituted (C₁-C₁₈)hydrocarbyl or the twoR^(C) are taken together to form a (C₂-C₁₉)alkylene, each R^(P) isunsubstituted (C₁-C₁₈)hydrocarbyl; and each R^(N) is unsubstituted(C₁-C₁₈)hydrocarbyl, a hydrogen atom or absent; R^(1a), R^(1b), or bothis a halogen atom; R^(2a) and R^(2b) independently is a hydrogen,(C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, N(R^(N))₂, NO₂, OR^(C),SR^(C), Si(R^(C))₃, Ge(R^(C))₃, CN, CF₃, F₃CO, halogen atom; and each ofthe others of R^(1a), R^(2a), R^(1b), and R^(2b) independently is ahydrogen, (C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, N(R^(N))₂,NO₂, OR^(C), SR^(C), Si(R^(C))₃, CN, CF₃, F₃CO or halogen atom; each ofR^(3a), R^(4a), R^(3b), R^(4b), R^(6c), R^(7c), R^(8c), R^(6d), R^(7d),and R^(8d) independently is a hydrogen atom; (C₁-C₄₀)hydrocarbyl;(C₁-C₄₀)heterohydrocarbyl; Si(R^(C))₃, Ge(R^(C))₃, P(R^(P))₂, N(R^(N))₂,OR^(C), SR^(C), NO₂, CN, CF₃, RCS(O)—, RCS(O)₂—, (RC)₂C═N—, RCC(O)O—,RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)— or halogen atom; each of R^(5c) andR^(5d) is independently a (C₆-C₄₀)aryl or (C₁-C₄₀)heteroaryl; and eachof the aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl,hydrocarbylene, and heterohydrocarbylene groups is independentlyunsubstituted or substituted with one or 5 more substituents R^(S); andeach R^(S) is independently a halogen atom, polyfluoro substitution,perfluoro substitution, unsubstituted (C₁-C₁₈)alkyl, F₃C—, FCH₂O—,F₂HCO—, F₃CO—, R₃Si—, R₃Ge—, RO—, RS—, RS(O)—, RS(O)₂—, R₂P—, R₂N—,R₂C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R₂NC(O)—, or two of theR^(S) are taken together to form an unsubstituted (C₁-C₁₈)alkylene,wherein each R independently is an unsubstituted (C₁-C₁₈)alkyl.

A wide variety of additional substitution may be present at all othercarbons of the at least four phenyl rings included within the catalystof formula (III) or such may have simply hydrogen. Some examples ofpreferred R^(5c) and R^(5d) substituents include3,5-di(tertiary-butyl)phenyl; 3,5-diphenylphenyl; 1-naphthyl,2-methyl-1-naphthyl; 2-naphthyl; 1,2,3,4-tetrahydronaphthyl;1,2,3,4-tetrahydro-naphth-5-yl; 1,2,3,4-tetrahydronaphth-6-yl;1,2,3,4-tetrahydroanthracenyl; 1,2,3,4-tetrahydroanthracen-9-yl;1,2,3,4,5,6,7,8-octahydroanthracenyl;1,2,3,4,5,6,7,8-octahydroanthracen-9-yl; phenanthren-9-yl;1,2,3,4,5,6,7,8-octahydrophenanthren-9-yl; 2,3-dihydro-1H-inden-6-yl;naphthalene-2-yl; 1,2,3,4-tetrahydronaphthalen-6-yl;1,2,3,4-tetrahydronaphthalen-5-yl; anthracen-9-yl;1,2,3,4-tetrahydroanthracen-9-yl;1,2,3,4,5,6,7,8-octahydro-anthracen-9-yl; 2,6-dimethylphenyl;2,6-diethylphenyl; 2,6-bis(1-methylethyl)phenyl; 2,6-diphenyl-phenyl;3,5-dimethylphenyl; 3,5-bis(tri-fluoromethyl)phenyl;3,5-bis(1-methylethyl)phenyl; 3,5-bis(1,1-dimethylethyl)phenyl;3,5-diphenyl-phenyl); 2,4,6-trimethylphenyl; and2,4,6-tris(1-methylethyl)phenyl); 1-methyl-2,3-dihydro-1H-inden-6-yl;1,1-dimethyl-2,3-dihydro-1H-inden-6-yl;1-methyl-1,2,3,4-tetrahydro-naphthalen-5-yl;1,1-dimethyl-1,2,3,4-tetrahydronaph-thalen-5-yl.1,2,3,4-tetrahydroquinolinyl; isoquinolinyl;1,2,3,4-tetrahydroisoquinolinyl; carbazolyl;1,2,3,4-tetrahydrocarbazolyl; 1,2,3,4,5,6,7,8-octahydrocarbazolyl;3,6-di(tertiary-butyl)-carbazolyl; 3,6-di(tertiary-octyl)-carbazolyl;3,6-diphenylcarbazolyl; 3,6-bis(2,4,6-trimethylphenyl)-carbazolyl;3,6-di(tertiary-butyl)-carbazol-9-yl;3,6-di(tertiary-octyl)-carbazol-9-yl; 3,6-diphenylcarbazol-9-yl;3,6-bis(2,4,6-trimethylphenyl)-carbazol-9-yl; quin-olin-4-yl;quinolin-5-yl; quinolin-8-yl; 1,2,3,4-tetrahydroquinolin-1-yl;isoquinolin-1-yl; isoquinolin-4-yl; iso-quinolin-5-yl; isoquinolin-8-yl;1,2,3,4-tetrahydroisoquinolin-2-yl; 1H-indol-1-yl; 1H-indolin-1-yl;9H-carbazol-9-yl; 1,2,3,4-tetrahydrocarbazolyl-9-yl;1,2,3,4,5,6,7,8-octahydrocarbazolyl-9-yl;4.6-bis(1,1-dimethylethyl)pyridine-2-yl; 4,6-diphenylpyridin-2-yl;3-phenyl-1H-indol-1-yl; 3-(1,1-dimethylethyl)-1H-indol-1-yl;3,6-diphenyl-9H-carbazol-9-yl;3,6-bis[2′,4′,6′-tris(1,1-dimethylphenyl)]-9H-carbazol-9-yl;3,6-bis(1,1-dimethyl-ethyl)-9H-carba-zol-9-yl.

In more particular embodiments, the catalyst may be selected from thecompounds represented by formulas (IV) to (X), shown in FIGS. 1-7.Additional moieties denoted by abbreviations include Me (methyl) andt-Bu (tert-butyl).

In carrying out the process of the invention it is desirable that thecontact between the olefins) and the coordination-insertion catalystoccur in a continuously-fed backmixed reactor zone. As the term is usedherein, “backmixed reactor zone” refers to an environment wherein areaction product is intermingled with unconverted reactor feeds. Acontinuous stirred tank reactor is preferred for this purpose, while itis noted that plug-flow reactors are specifically designed to preventback-mixing. However, a loop reactor can accomplish a variable degree ofbackmixing by recycling a portion of reactor effluent to the feed of aplug-flow zone, with the recycle ratio moderating the degree ofbackmixing. Thus, plug-flow reactors are non-preferred, while a loopreactor with a plug flow zone is preferred. In the inventive processbackmixing ensures reaction of already-produced oligomers with newfeedstock, e.g., ethylene. It is this continuous contact that enablesthe oligomers to become branched via repeated olefin insertion.

Conditions under which the contact occurs in the continuously-fed,backmixed reactor zone may include a temperature desirably ranging from0° C. to 250° C., more desirably from 25° C. to 200° C., and mostdesirably from 50° C. to 180° C.; an ethylene partial pressure desirablyranging from 15 psi (pounds per square inch, 103 kilopascals, kPa) to500 psi (3450 kPa), more desirably from 30 psi (207 kPa) to 300 psi(2070 kPa), and most desirably from 50 psi (345 kPa) to 200 psi (1380kPa); and a residence time desirably ranging from 1 minute (min) to 120min, more desirably from 5 min to 60 min, and most desirably from 10 minto 30 min. A reactor system may be comprised of many low residence timereaction zones or a few high residence time reaction zones. Nonetheless,those skilled in the art will easily understand that alteration ofparameters may be employed for reasons of convenience, alteration ofyield, avoidance of undesirable side products or degradation, and thelike.

In order to prepare the homo-oligomers or co-oligomers of the invention,the starting olefin and/or the selected alpha-olefin monomer(s) is/arefed into a suitable reactor, for batch, semi-continuous, or continuousproduction, wherein such olefins) will come into contact with thecatalyst. In the case of preparation of co-oligomers, it is noted thatthe ethylene/alpha-olefin reactivity ratio is distinct for any givencatalyst and provides a methodology to determine the amount ofalpha-olefin that will be required to attain a targeted co-oligomercomposition. Reactivity ratios may be determined using well knowntheoretical techniques or empirically derived from actual polymerizationdata. Suitable theoretical techniques are disclosed, for example, in B.G. Kyle, Chemical and Process Thermodynamics, 3^(rd) ed., Prentice-Hall(1999) and in Soave, Giorgio. “Equilibrium constants from a modifiedRedlich-Kwong equation of state”, Chemical Engineering Science, Vol. 27,Issue 6, June 1972, pp. 1197-1203. Commercially available softwareprograms may be used to assist in deriving reactivity ratios fromexperimentally derived data. One example of such software is Aspen Plusfrom Aspen Technology, Inc., Ten Canal Park, Cambridge, Mass.02141-2201, USA.

The metal-ligand complex discussed above is rendered catalyticallyactive by contacting it to, or combining it with, the activatingco-catalyst or by using an activating technique such as those that areknown in the art for use with metal-based olefin polymerizationreactions. Suitable activating co-catalysts for use herein include alkylaluminums; polymeric or oligomeric alumoxanes (also known asaluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating,ion-forming compounds, including but not limited to the use of suchcompounds under oxidizing conditions. A suitable activating techniquemay be bulk electrolysis. Combinations of one or more of the foregoingactivating co-catalysts and/or techniques are also contemplated. Theterm “alkyl aluminum” means a monoalkyl aluminum dihydride ormonoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkylaluminum halide, or a trialkylaluminum. Alumoxanes and theirpreparations are described in, for additional understanding, U.S. Pat.No. 6,103,657. Examples of preferred polymeric or oligomeric alumoxanesare methylalumoxane, triisobutylaluminum-modified methylalumoxane, andisobutylalumoxane. Such may be employed such that the ratio of totalnumber of moles of the one or more metal-ligand complexes of formula(III) to total number of moles of activating co-catalyst is preferablyfrom 1:10,000 to 100:1.

A variety of homo-oligomerization or co-oligomerization conditions andcombinations thereof may be employed, according to the startingmaterials, nature of the reaction (batch, semi-continuous, orcontinuous), apparatus set-up, desired products, and so forth. However,in general, suitable oligomers or co-oligomers of the invention may beproduced using one or more of the specified catalyst selections at atemperature ranging from 20 degrees Celsius (° C.) to 220° C., andpreferably 100° C. to 200° C., for a time preferably ranging from 10minutes (min) to 300 min. Other parameters, such as pressure, may becontrolled within ranges known to those skilled in the art and are notgenerally considered to be critical to practice of the presentinvention, but may be varied according to the desires and needs of thepractitioner. It is usually preferred to carry out the process as acontinuous process, using at least one continuous stir tank reactor(CSTR) or other suitable vessel(s).

The oligomerization process generates an oligomer (in some embodimentsthe hydrophobe) with a specific structure. In the desired fraction, themain carbon chain contains an average of preferably between 0.5 and 2.5branches. The branches are predominantly (greater than 50%) ethylbranches, preferably greater than 80% ethyl branches. Finally, thebranches are located more than one carbon away from each end of the mainchain in more than 20% of the molecules on average, preferentially inmore than 40% on average. Furthermore, the branches (on the oligomer)are situated at the C2 carbon (relative to the unsaturated chain end) inless than 40% of the molecules on average, preferably in less than 25%on average. Finally, the oligomer may contain a vinyl olefin, avinylidene olefin, or a vinylene olefin. The oligomer product containsgreater than 50% vinyl olefin, preferably greater than 70% vinyl olefin.

The preparation of the alcohol is carried out via hydroformylationfollowed by hydrogenation. Hydroformylation/hydrogenation to generate aprimary alcohol may add more branching (i.e., a methyl branch at the C2position relative to the alcohol) to the olefins oligomer with vinylgroups depending on the selectivity of the hydroformylation catalyst(i.e. whether hydroformylation occurs mostly at the C1 position of theolefin (little added branches relative to the corresponding olefinoligomer) or at the C2 position of the olefin (methyl branchintroduced)). A rhodium catalyst with an organophosphorus ligand may beused for hydroformylation of the oligomer product. The organophosphorusligand may be, for example, the one shown in FIG. 8 fortris(2,4-di-tert-butylphenyl)phosphite (L).

During hydroformylation, different types of olefins lead to variousstructures for related aldehydes. The aldehydes contain one carbon atommore than the starting olefins.

Subsequent hydrogenation of the aldehydes to the corresponding alcoholsmay be performed with hydrogen in the presence of a hydrogenationcatalyst. For example, hydrogenation can be performed using platinumgroup metal catalysts or a nickel catalyst. The catalysts can besupported on activated carbon, silica or alumina or unsupported.

The alcohol product may comprise a main carbon chain containing anaverage of between 0.5 and 2.5 branches, wherein more than 50% of thebranches are ethyl branches, wherein the branches are located more thanone carbon away from each end of the main carbon chain in more than 20%of alcohol product molecules.

The process may further include the reaction of the alcohol with analkylene oxide in the presence of a catalyst to generate nonionicalkoxylated surfactants. The alkylene oxide may be any epoxide withcarbon numbers ranging from C2-C12. Preferably, the alkylene oxide isethylene oxide, 1,2-epoxypropane, or 1,2-epoxybutane. Further, thealkoxylation step may involve alkoxylation of more than one type ofalkylene oxide, as is known in the art. Also, each initiator may bealkoxylated by 1 to 100 alkylene oxide molecules, preferably by 1 to 20alkylene oxide molecules, which may be all the same or a mixture ofdifferent alkylene oxides in a random or block configuration. Thealkoxylation catalyst or catalyst precursor may be any catalyst knownfor alkoxylation reactions (as described in Alkylene Oxides and TheirPolymers, Surfactant Science Series, Vol. 35, Ed. by F. E. Bailey, Jr.and Joseph V. Koleske, Marcel Dekker, Inc., New York, 1990). Preferredexamples are alkali metal hydroxides, like sodium hydroxide, potassiumhydroxide, alkali earth metal hydroxide, alkali metals, like sodium orpotassium, potassium hydride, and DMC (double metal cyanide) catalysts.The alkoxylation reaction may be conducted in a solvent or withoutsolvent. The solvent can be any solvent suitable for use in alkoxylationreactions. It is preferable that the solvent be capable of dissolvingthe reactants. Examples of solvents include dimethoxyethane, THF,1,4-dioxane, diglyme, and tetraglyme.

The nonionic alkoxylated surfactants may further be sulfated to producean anionic ether sulfate surfactant product. In an alternativeembodiment, the alcohol may be sulfated to produce an anionic sulfatesurfactant product.

In an alternative embodiment, instead of hydroformylating the oligomerolefin, the oligomer olefin may instead be sulfonated to generateanionic sulfonated surfactants.

Due to the composition of the oligomer (i.e. vinyl, vinylidene andvinylene olefins), the product is a mixture of lightly branched alphaolefin sulfonates (AOS) and internal olefin sulfonates (IOS).

The final lightly branched surfactant product may comprise a main carbonchain containing an average of between 0.5 and 2.5 branches, whereinmore than 50% of the branches are ethyl branches, wherein the branchesare located more than one carbon away from each end of the main carbonchain in more than 20% of surfactant product molecules.

The final nonionic products (nonionic surfactants) should be able toreduce the surface tension of water. For a 0.1 wt % aqueous solution,the equilibrium surface tension should be less than 50 mN/m and thecontact angle on a PTFE film should be less than 75 degrees. Furthersurfactant performance requirements may be obtained in other similarapplications for nonionic and anionic surfactants.

Possible applications of the nonionic and anionic surfactants generatedinclude household and industrial cleaning, personal care, paints &coatings, emulsion polymerization, agriculture, oil & gas, textileprocess, food processing, lubricant and fuel additives, leatherprocessing and mining.

EXAMPLES

Various examples are demonstrated.

Example 1: Ethylene Oligomerization Catalyst Preparation

Analytical Measurements

For ¹³C NMR experiments, samples are dissolved in 10 mm NMR tubes inchloroform-d with 0.02 M Cr(acac)₃ added. The typical concentration is0.50 g/2.4 mL. The tubes are then heated in a heating block set at 50°C. The sample tubes are repeatedly vortexed and heated to achieve ahomogeneous flowing fluid. For samples with visible wax present,tetrachloroethane-d₂ is used as the solvent instead of chloroform-d, andthe sample preparation temperature is 90° C.

¹³C NMR spectra are taken on a Bruker Avance 400 MHz spectrometerequipped with a 10 mm cryoprobe. The following acquisition parametersare used: 5 seconds relaxation delay, 90 degree pulse of 13.1 μs, 256scans. The spectra are centered at 80 ppm with a spectral width of 250ppm. All measurements are taken without sample spinning at either 50° C.(for chloroform solutions) or 90° C. (for tetrachloroethane solutions).The ¹³C NMR spectra are referenced to 77.3 ppm for chloroform or 74.5ppm for tetrachloroethane.

Catalyst Synthesis

Preparation of 2-(2-bromoethoxy)-1,5-difluoro-3-iodobenzene

16.55 g (64.65 mmol) of 2-iodo-4,6-difluorophenol, 86.232 g (459.02mmol) of 1,2-dibromoethane, 29.5 g (213.35 mmol) of potassium carbonateand acetonitrile (85 mL) is place in a 250 mL round bottom flask. Thereaction is shown in FIG. 9. The suspension is stirred at 60° C. undernitrogen overnight. The reaction is filtered and the organic solution isconcentrated. The residue is run through a 220 g ISCO column eliminatingone impurity and the remaining 1,2-dibromoethane. The product is 18.22 gof a colorless oil (77.6% Yield). ¹H NMR (400 MHz, Chloroform-d) δ 7.30(ddd, J=7.4, 3.0, 2.0 Hz, 1H), 6.89 (ddd, J=10.7, 8.1, 2.9 Hz, 1H),4.34-4.29 (m, 2H), 3.70-3.65 (m, 2H). ¹³C NMR (101 MHz, cdcl₃) δ 159.63,159.52, 157.03, 152.62, 121.06, 105.73, 91.48, 73.44, 73.40, 28.97. ¹⁹FNMR (376 MHz, Chloroform-d) δ −114.47 (tt, J=7.6, 3.4 Hz), −122.18 (dd,J=10.7, 3.0 Hz).

Preparation of2-(2-(2,4-difluoro-6-iodophenoxy)ethoxy)-5-fluoro-1-iodo-3-methylbenzene

150 mL of acetone, 3.768 g (27.261 mmol) of potassium carbonate, 6.00 g(16.036 mmol) of 1-(2-bromoethoxy)-2,4-difluorobenzene, and 4.041 g(16.036 mmol) of 2-iodo-4-fluoro-6-methylphenol is added to a 250 mLround bottom flask under nitrogen. The reaction is shown in FIG. 10. Thesolution is heated to reflux overnight. Gas chromatography (GC) confirmsfull conversion to product, so the reaction mixture is cooled, filteredand the filtrate was concentrated. The residue is dissolved in methylenechloride, washed with brine, dried over magnesium sulfate, andrecrystallized from acetonitrile. The solid is then run through a 330 gISCO column using a hexanes:ethyl acetate gradient. The oil is thenrecrystallized to yield 4.23 g of the product (49.4% Yield).

¹H NMR (400 MHz, Chloroform-d) δ 7.31 (ddt, J=7.4, 3.0, 2.2 Hz, 2H),6.93-6.86 (m, 2H), 4.44 (ddd, J=6.0, 3.9, 1.0 Hz, 2H), 4.23 (ddd, J=5.5,4.2, 0.6 Hz, 2H), 2.40 (s, 3H).

¹³C NMR (101 MHz, cdcl₃) δ 159.80, 159.44, 159.33, 157.34, 156.96,156.84, 155.30, 155.18, 153.20, 153.17, 152.78, 152.65, 143.73, 143.69,143.61, 143.57, 133.59, 133.50, 123.51, 123.27, 121.27, 121.23, 121.03,120.99, 118.08, 117.85, 91.47, 91.44, 91.36, 91.34, 91.14, 91.05, 72.90,72.86, 71.53, 17.45, 17.44.

¹⁹F NMR (376 MHz, Chloroform-d) δ −115.24 (td, J=7.7, 3.7 Hz),−117.55-−117.74 (m), −122.11 (dt, J=10.8, 2.7 Hz).

Preparation of3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-2′-(2-((3′-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,5-difluoro-2′-hydroxy-5′-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-yl)oxy)ethoxy)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol

1,2-dimethoxyethane (67 mL) is added to 4.00 g (5.725 mmol) of3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole,1.482 g (2.719 mmol) of2-(2-(2,4-difluoro-6-iodophenoxy)ethoxy)-5-fluoro-1-iodo-3-methylbenzene,a solution of NaOH (0.6870 g) in water (16 mL) and THF (40 mL) in athree neck 250 mL round bottom flask. The reaction is shown in FIG. 11.The reaction mixture is sparged with N₂ for 15 minutes then 0.1322 g(0.1145 mmol) of Pd(PPh₃)₄ is added. Upon addition the reaction mixtureis heated to 85° C. overnight. The reaction mixture is then concentratedwith the residue being taken up in methylene chloride (200 mL), washedwith brine (200 mL), dried over anhydrous magnesium sulfate, filteredthrough a pad of silica gel, and concentrated to afford crude protectedligand. THF (50 mL), methanol (50 mL) and PTSA is added to the crudeprotected ligand until the solution is acidic. The solution is heated to60° C. overnight, then cooled and concentrated. The crude ligand istaken up in methylene chloride (100 mL), washed with brine (100 mL),dried with anhydrous magnesium sulfate, filtered through a pad of silicagel then concentrated to afford ligand as an off white crystallinepowder. Thin layer chromatography (TLC) shows impurities, so the ligandis run through a 330 g column using solid phase loading and a ethylacetate:hexanes gradient. The appropriate fractions are concentrated andplaced under vacuum overnight to afford 2.7 g of white crystals (79.7%Yield).

¹H NMR (400 MHz, Chloroform-d) δ 8.14 (d, J=7.7 Hz, 4H), 7.43-7.16 (m,9H), 7.06-6.79 (m, 8H), 6.06 (d, J=1.7 Hz, 1H), 5.58 (d, J=1.9 Hz, 1H),4.04 (t, J=4.8 Hz, 2H), 3.78 (t, J=4.8 Hz, 2H), 2.04 (d, J=1.8 Hz, 3H),1.70-1.63 (m, 4H), 1.44 (dd, J=8.6, 1.7 Hz, 36H), 1.28 (d, J=27.3 Hz,12H), 0.75 (s, 16H).

¹³C NMR (101 MHz, CDCl₃) δ 160.25, 159.14, 157.83, 156.82, 156.75,156.70, 156.62, 149.78, 149.76, 147.60, 147.42, 143.33, 143.30, 143.13,143.03, 142.55, 140.46, 140.43, 140.35, 140.31, 139.68, 139.43, 139.40,134.36, 134.33, 134.26, 134.23, 133.94, 133.86, 133.04, 132.95, 128.78,128.74, 127.52, 127.28, 126.17, 126.15, 125.42, 124.96, 124.93, 124.91,124.68, 124.05, 123.74, 123.60, 123.56, 123.53, 123.40, 117.39, 117.17,116.43, 116.35, 116.10, 115.87, 113.65, 113.62, 113.41, 109.32, 109.26,104.73, 104.47, 104.24, 72.74, 72.70, 72.26, 57.03, 56.95, 38.22, 38.20,34.74, 32.44, 32.42, 32.14, 32.10, 32.05, 31.93, 31.87, 31.69, 31.62,31.52, 31.46, 30.38, 16.39.

¹⁹F NMR (376 MHz, Chloroform-d) δ −115.26 (dt, J=8.7, 4.1 Hz), −117.94(t, J=8.7 Hz), −124.48 (dd, J=11.1, 4.2 Hz).

Preparation of(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-2′-(2-((3′-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,5-difluoro-2′-hydroxy-5′-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-yl)oxy)ethoxy)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol)dimethyl-zirconium

A 20 mL vial is charged with ZrCl₄ (0.119 g, 0.509 mmol) and toluene (10mL) and cooled to −35° C. MeMgBr (3M solution in ether, 0.66 mL, 1.98mmol) is added to the solution. The reaction is shown in FIG. 12. Thesolution quickly turns to a dark color. After 5 min of stirring thesolution is treated with a −35° C. toluene (7 mL) solution of3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-2′-(2-((3′-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,5-difluoro-2′-hydroxy-5′-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-yl)oxy)ethoxy)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol(0.615 g, 0.494 mmol). The solution is allowed to stir for 3 hours, thenthe solution is passed through a filter frit. The solids are washed withtoluene and all volatiles are removed in vacuo leaving a white solid.The white solid is dissolved in hexanes and passed through a 0.45 micronfrit. All volatiles are removed and the crude solid is checked by ¹H NMRand used without further purification. Yield 91% (0.610 g).

¹H NMR (400 MHz, C₆D₆) δ 8.21-8.40 (m, 4H), 7.96-8.00 (m, 1H), 7.85 (d,1H), 7.61-7.72 (m, 3H), 7.48-7.50 (m, 2H), 7.28-7.34 (m, 3H), 7.17 (d,1H), 6.86-7.10 (m, 3H), 6.65-6.68 (m, 1H), 6.19-6.22 (m, 1H), 3.76-3.77(m, 2H), 2.65-2.73 (m, 2H), 1.54-1.62 (m, 4H), 1.50 (s, 9H), 1.49 (s,9H), 1.35 (s, 9H), 1.31 (s, 9H), 1.18-1.29 (m, 12H), 0.99 (s, 3H), 0.80(s, 9H), 0.76 (s, 9H), −0.76 (s, 3H), −0.96 (s, 3H).

¹³C{¹H} NMR (101 MHz, C₆D₆) δ 155.9, 155.6 (d), 153.4, 153.1 (d), 148.5(d), 148.1, 147.1, 142.1 (d), 137.4, 137.1, 136.9, 136.6, 135.7, 135.6,134.6, 134.2, 134.1 (d), 134.0, 131.1 (dd), 130.9 (d), 123.9, 123.8,123.0, 122.9, 121.5, 121.3, 120.1, 119.4, 119.3, 119.2, 118.3, 118.2,117.0, 117.1, 112.6, 112.3, 111.5, 111.5, 111.2, 111.0, 110.5 (d),108.7, 108.5, 107.6 (d), 105.5 (d), 103.9, 97.9 (d), 97.6 (d), 64.7,64.6, 52.0, 51.7, 37.4, 36.4, 36.3, 32.9, 32.8, 29.5, 29.5, 29.4, 29.3,27.1, 27.1, 27.0, 26.9, 26.9, 26.8, 26.7, 26.6, 26.5, 25.7 (br m), 17.5,10.4, 8.9.

¹⁹F NMR (376 MHz, C₆D₆) δ −110.55 (m), −115.33 (m), −119.54 (m).

Example 2: Ethylene Oligomerization

Semi-Batch Oligomerizations

Oligomerizations are conducted in a 2 L Parr™ batch reactor. The reactoris heated by an electrical heating mantle, and is cooled by an internalserpentine cooling coil containing cooling water. Both the reactor andthe heating/cooling system are controlled and monitored by a Camile™ TGprocess computer. The bottom of the reactor is fitted with a dump valve,which empties the reactor contents into a stainless steel dump pot,which is prefilled with a catalyst kill solution (typically 5 mL of anIrgafos™/Irganox™/toluene mixture).

The dump pot is vented to a 30 gallon blowdown tank, with both the potand the tank N₂ purged. All chemicals used for oligomerization orcatalyst makeup are run through purification columns to remove anyimpurities that may affect oligomerization. Liquid feeds such asalpha-olefin and solvents are passed through two columns, the firstcontaining Al₂O₃ alumina, the second containing Q5, which is a copperreactant to scrub oxygen. Ethylene feed is passed through two columns,the first containing Al₂O₃ alumina and 4 Angstroms (Å) average pore sizemolecular sieves to remove water, the second containing Q5 reactant. TheN₂, used for transfers, is passed through a single column containingAl₂O₃ alumina, 4 Å average pore size molecular sieves, and Q5 reactant.

The reactor is loaded first from the shot tank containing toluene. Theshot tank is filled to the load set points by use of a lab scale towhich the shot tank is mounted. After liquid feed addition, the reactoris heated up to the polymerization temperature set point. Ethylene isadded to the reactor when at reaction temperature to maintain reactionpressure set point. Ethylene addition amounts are monitored by amicro-motion flow meter and integrated to give overall ethylene uptakeafter catalyst injection.

The catalyst and bis(octadecyl)methylammoniumtetrakis(pentafluorophenyl) borate ([HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄]) (BOMATPB)activator are mixed with the appropriate amount of purified toluene toachieve a desired molarity solution. The catalyst and activator arehandled in an inert glove box, drawn into a syringe and pressuretransferred into the catalyst shot tank. This is followed by threerinses of toluene, 5 mL each. Immediately after catalyst addition therun timer begins. Ethylene is then added continuously by the Camile™ tomaintain reaction pressure set point in the reactor. If the ethyleneuptake rate is low, then the headspace is purged, more catalyst andactivator are added, and the ethylene pressure is re-established. Aftera designated time or ethylene uptake the agitator is stopped and thebottom dump valve opened to empty reactor contents to the dump pot. Thedump pot contents are poured into a round bottom flask and all C8 andbelow volatiles were removed via rotary evaporation (80° C./20 Torr).

Example 3: Fractionation

A Vigreux column and short path distillation head are equipped onto theround bottom flask and the crude product is first distilled at 50°C./500 mTorr to remove the ˜C10 components. Next, the heating bath israised to 100° C. (300 mTorr) and the ˜C12 fractions are collected,followed by the ˜C14 fractions at 135° C. (200 mTorr). The Vigreuxcolumn is then removed and the ˜C16 fractions can be collected at 100°C./100 mTorr. Distillation of the desired products may be done atvarious temperature/pressures and those skilled in the art willrecognize the importance of theoretical plates on the degree ofseparation.

A series of semibatch oligomerizations are performed with3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-2′-(2-((3′-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,5-difluoro-2′-hydroxy-5′-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-yl)oxy)ethoxy)-5′-fluoro-3′-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol-zirconiumdimethyl(Formula (VI)) catalyst at 60° using toluene as a reaction solvent(Table 1 below). The semibatch nature of the reaction is due to thecontinuous feeding of ethylene gas to maintain a constant pressure, andexcess butene is purged out to allow the continued consumption ofethylene. No alpha-olefin comonomers are added to the reaction. Theaverage number of carbons per product oligomer is calculated assumingall molecules have a single unsaturation group.

TABLE 1 Run MMAO- Exo- Ethylene Run Temp Toluene Press Time CatalystRIBS-2 3A Therm (g) (g) # (*C.) (g) (psi) (min) Name μmoles Metal μmolesμmoles (*C.) Initial Added 1 60 300 116 164.6 Formula 16.9 Zr 20.28 107.6 21.6 120 VI 2 60 300 116 226.9 Formula 39.9 Zr 39.9 10 2.2 19.4220.6 VI

TABLE 2 Branching Detailed Degree position Average of branching Conc. ofunsaturation (relative to Average # of (Including chain ends) Vinylunsat. Chain MW branches Hexyl Butyl Ethyl Methyl Vinylene V1 V3Vinylidene ends) Mn (per chain) (per chain) (per chain) C2 C4 C12fraction- 167 0.80 0.66 0.29 0.86 0.01 0.03 0.39 0.43 0.17 17% 42% Run#1 C14 fraction- 185 0.91 0.66 0.33 0.96 0.01 0.03 0.35 0.45 0.17 17%45% Run #1 C16 fraction- 216 1.12 0.70 0.39 1.12 0.01 0.04 0.30 0.460.17 17% 48% Run #1 C12 fraction- 164 0.82 0.63 0.31 0.88 0.01 0.03 0.370.43 0.19 18% 42% Run #2 C14 fraction- 180 0.91 0.63 0.33 0.98 0.01 0.030.33 0.45 0.19 19% 45% Run #2 C16 fraction- 210 1.10 0.70 0.38 1.08 0.010.04 0.31 0.46 0.19 19% 46% Run #2

Determination of the characterizing properties listed above in Table 2may be accomplished as follows:

For ¹³C NMR measurement, product samples are dissolved in 10 millimeter(mm) nuclear magnetic resonance (NMR) tubes in chloroform-d₁ (deuteratedchloroform) to which 0.02 molar (M) chromium acetylacetonate, Cr(acac)₃,is added. The typical concentration is 0.50 grams per 2.4 milliliter(g/mL). The tubes are then heated in a heating block set at 50° C. Thesample tubes are repeatedly vortexed and heated to achieve a homogeneousflowing fluid. For samples with visible wax present,tetrachloroethane-d₂ (deuterated tetrachloroethane) is used as thesolvent instead of chloroform-d₁, and the sample preparation temperatureis 90° C. ¹³C NMR spectra are taken on a Bruker Avance 400 megaherz(MHz) spectrophotometer equipped with a 10 mm cryoprobe. The followingacquisition parameters are used: 5 seconds relaxation delay, 90 degreepulse of 13.1 milliseconds, 256 scans. The spectra are centered at 80parts per million (ppm) with a spectral width of 250 ppm. Allmeasurements are taken without sample spinning at either 50° C. (forchloroform-d₁ solutions) or 90° C. (for tetrachloroethane-d₂ solutions).The ¹³C NMR spectra are referenced to 77.3 ppm for chloroform-d₁ or 74.5ppm for tetrachloroethane-d₂.

Example 4: Hydroformylation of C12 Olefins to C13 Aldehydes

Rh(CO)₂(acac) (15.1 mg; 0.0585 mmol),tris(2,4-di-tert-butylphenyl)phosphite (757 mg; 1.17 mmol) and toluene(20 g) are placed in a 50 mL nitrogen purged bottle with a septum. Themixture is stirred until the components dissolved to form a yellowsolution. The solution is transferred by syringe into a 150 mL Parrreactor under nitrogen, then purged three times with syngas (1:1) at 100psi with stirring and activated at 90° C. and 100 psi of syngas (1:1)for about 1 h. Then the syngas is vented and the starting C12 olefinfeedstock (9.39 g) is quickly added to the reactor via syringe. Thereaction is carried out for two hours at 100° C. and then analyzed by ¹HNMR. The olefin signals at about 2 ppm and 4.5-6 ppm disappeared and newsignals of aldehyde protons appeared at 9.5-10 ppm, suggesting that thereaction is complete. Toluene is removed under reduced pressure and thealdehydes are separated from the catalyst and the ligand by vacuumdistillation at 57° C./127 mm Hg to give 7.46 g of the aldehyde product.

Example 5: Hydrogenation of the C13 Aldehydes

A distilled aldehyde product from the previous example (7.46 g) isdissolved in 20 mL of anhydrous THF and hydrogenated in a 150 mL Parrreactor at 500 psi and 100° C. using 0.75 g of 5% Ru/C catalyst fromStrem Chemical. The reaction is followed by hydrogen pressure drop. ¹HNMR analysis indicates in four hours that no residual aldehyde remains.The mixture is filtered, the catalyst washed with 5 mL×2 of THF and thecombined solutions are evaporated in vacuum to give 7.18 g of thealcohol product.

Example 6: Hydroformylation of C14 Olefins to C15 Aldehydes

Rh(CO)₂(acac) (25.0 mg; 0.0969 mmol),tris(2,4-di-tert-butylphenyl)phosphite (1.161 g; 1.79 mmol) and toluene(20 g) are placed in a 50 mL nitrogen purged bottle with a septum. Themixture is stirred until the components dissolved to form a yellowsolution. The solution is transferred by syringe into a 150 mL Parrreactor under nitrogen, then purged three times with syngas (1:1) at 100psi with stirring and activated at 90° C. and 100 psi of syngas (1:1)for about one hour. Then the syngas is vented and the starting C14olefin feedstock (15.03 g) is quickly added to the reactor via syringe.The reaction is carried out for two hours at 100° C. and then analyzedby ¹H NMR. The olefin signals at about 2 ppm and 4.5-6 ppm disappear andnew signals of aldehyde protons appear at 9.5-10 ppm, suggesting thatthe reaction is complete. Toluene is removed under reduced pressure andthe aldehydes are separated from the catalyst and the ligand by vacuumdistillation at 68° C./202 mm Hg to give 11.99 g of the aldehydeproduct.

Example 7: Hydrogenation of the C15 Aldehydes

A distilled aldehyde product from the previous example (11.99 g) isdissolved in 50 mL of anhydrous THF and hydrogenated in a 150 mL Parrreactor at 500 psi and 100° C. using 1.2 g of 5% Ru/C catalyst fromStrem Chemical. The reaction is followed by hydrogen pressure drop. ¹HNMR analysis indicates in four hours that no residual aldehyde remains.The mixture is filtered, the catalyst washed with 10 mL×2 of THF and thecombined solutions are evaporated in vacuum to give 11.80 g of thealcohol product. The characterizing properties of the C13 and C15alcohol products are listed below in Table 3.

TABLE 3 Detailed Degree of branching Average (Including chain ends)Branching position Average # of Quarter- (relative to hydroxyl group) MWbranches Methyl Ethyl Propyl Butyl Longer nary C2 Mn (per chain) (perchain) >=C4 C3 Methyl Ethyl Longer C13 Alcohol 175 1.27 0.17 0.32 0.050.21 0.26 0.0 41% 6% 36% 6% 12% C15 Alcohol 203 1.58 0.14 0.29 0.08 0.220.27 0.0 38% 4% 33% 6% 19%

Example 8: Ethoxylation of the C13 and C15 Alcohols

The reactions are carried out in a Symyx PPR® (Parallel PressureReactor) setup using twelve small reactors. The MFRM-331448 libraryinvolves ethoxylation of the alcohols with ethylene oxide (EO). Thelibrary layout was designed using Library Studio®.

Ethylene oxide (EO) is delivered via an Isco syringe pump equipped witha robotically controlled needle and compressed gas micro-valve connectedto the Symyx PPR®. Glass inserts along with removable PEEK stir paddlesfor each of twelve cells are dried in a vacuum oven at 125° C.overnight. The starter solutions after dissolution of potassium (1 wt %)are charged manually into the glass inserts under nitrogen using apipette. The amounts of starting alcohols are 4 mmol for all cases(Table 3).

All reagents are delivered by pipette into glass inserts and the mass ofmaterial in each inset is recorded. The inserts with reagents are loadedinto the corresponding PPR wells, the reactor modules are sealed, heatedto 60° C., and pressurized with 50 psi nitrogen. The correspondingtwelve cells are charged with calculated amounts of EO. The temperatureis then increased to 150° C. and the reaction mixtures are stirred forthree hours at that temperature. The reactors are then cooled, and thecells are vented and purged with nitrogen to remove residual EO. Aftercooling to room temperature, the glass inserts are removed from thereactors, the weights of the glass inserts are taken, and the productyields are calculated. The materials are analyzed by ¹H NMR and thenumber of EO equivalents for each product are determined (Table 4).

TABLE 4 Average EO Number of ROH EO equiv carbons in weight addedProduct by ¹H Sample ROH (g) (g) yield (g) NMR 1 C13 0.813 0.805 1.6164.9 2 C13 0.813 1.283 2.094 6.8 3 C13 0.813 2.289 3.100 14.6 4 C15 0.9251.098 2.023 7.0 5 C15 0.925 1.710 2.635 10.1 6 C15 0.925 2.332 3.25714.3

Example 9: Surface Properties of Surfactants

Surface Tension

The surface tension of a surfactant solution is measured using KrussK100 Surface Tensiometer fitted with a Wilhelmy platinum plate atambient temperature (21-22° C.). Deionized water is used to make thesolutions and the surface tension of the water is measured to be between72 and 73 mN/m. The result is reported as a mean of five repeatedtesting values with the standard deviation <0.1 mN/m.

Ross-Miles Foam Test

Ross-Miles Foam test is conducted as described by ASTM method D1173“Standard Test Method for Foaming properties of Surface Active Agents.”A glass pipet (“foam pipet”) is charged with 200 ml of the 0.1% aqueoussurfactant solution, while the graduated glass tube (“foam receiver”)with ID=5.0 cm is filled with 50 ml of the same solution. Aftercentering the pipet above the foam receiver, the aqueous solution in thepipet is allowed to drain 90 cm through air and splash into the solutionin the foam receiver, thereby forming foam. The height of the foamlayer, a measure of the volume of air which is incorporated into thefoam, was recorded at zero seconds, and at five minutes. Twomeasurements are made for each system at the ambient temperature andresult is reported as the mean.

Draves Wetting Time

Draves Wetting time is tested following the procedures of ASTM D 2281-68(Standard Test Method for Evaluation of Wetting Agents by the SkeinTest). All the tests are carried out at 0.1 weight percent concentrationof surfactant and at room temperature.

Contact Angle

Contact angle measurements are performed at ambient temperatureutilizing Kruss DSA-100 Drop Shape Analyzer. The instrument has amovable sample stage. Kruss software, DSA3.exe, controlled operation ofthe instrument and performed data analysis. The contact anglemeasurements is performed on a static sessile (i.e. sitting) drop.Teflon® tape (pink thread seal tape purchased from Lowes) or parafilm iscarefully placed on glass microscope slide, using a small amount ofadhesive on the each edge of the microscope slide to hold the Teflontape on the surface. Variability in surface composition and uniformitycan significantly affect the contact angle measurement, thus, extremecare is used when placing tape on a slide so that the tape, film, orpaper is not stretched or touched. The substrate was placed on a samplestage, and five liquid drops are deposited on the substrateprogrammatically, using the procedure predefined via DSA software. Anautomated procedure is utilized, as the drop volume, dispense rate, andneedle height can affect the drop shape, and thus, the contact anglemeasurement. In this study, drop volume was 5 μL, rate of dropdeposition was 6 μL/min, and measurement was made immediately after dropplacement. Once the drop image is taken, the baseline is determined,left and right contact angles are determined by software, and thearithmetic mean of left and right contact angles is calculated for eachdrop. The result is reported as mean of the values from three groups oftesting total fifteen drops.

The test results are summarized in Table 5 below. Two commercialproducts, Lutensol AO-7 (7 EO adduct of C13-C15 oxo alcohol) andLutensol TO-7 (7EO adduct of iso-tridecanol) from BASF are included forcomparison. The experimental samples demonstrate good surfactancy,reducing surface tension to about 30 mN/m with cmc lower than 100 ppm.Sample 1, which has similar amount EO adduction as the two commercialproducts, shows almost identical surface tension as the two commercialproducts, and demonstrates better wetting than Lutensol AO-7 and similarto Lutensol TO-7, a highly branched alcohol with low biodegradability.

TABLE 5 Ross Miles Draves Contact Foam Wetting angle ST (0.1 (0.1 wt %)(0.1 (degree) cmc wt %) 0 5 wt %) (0.1 wt %) Sample (ppm) mN/m min.(sec.) PTFE Parafilm 1-C13 36 28.2 30 30 26 59 50 2-C13 35 27.8 110 11018 55 49 3-C13 96 31.4 128 120 188 83 71 4-C15 10 28.8 80 80 56 63 615-C15 10 30.4 110 110 70 70 64 6-C15 17 33.4 120 120 228 77 72 LutensolAO-7 6 27.9 85 85 47 62 58 Lutensol TO-7 19 27.3 65 60 13 53 46

Example 10: Biodegradability Test of the Surfactant Samples

The ready biodegradability of the Experimental surfactant samples isevaluated using the OECD guideline 301F: Manometric Respirometry test.Biodegradation of each material is determined at an initialconcentration of approximately 50 mg/L, yielding approximately 100 mg/Ltheoretical oxygen demand (ThOD) in the test mixtures. The testchemicals are added to biodegradation test mixtures containing a definedmineral medium, which is inoculated with activated sludge (30 mg/L drysolids) from a municipal wastewater treatment facility (Midland, Mich.USA). This facility treats an excess of 11 million L/day of apredominantly domestic (>90% vol.) wastewater. Oxygen consumption andCO₂ evolution resulting from biodegradation of the test chemicals aremeasured over twenty-eight days using a Columbus InstrumentsMicroOxymax® respirometer system. In addition, removal of dissolvedorganic carbon (DOC) from the biodegradation test mixtures is determinedafter twenty-eight days. The results are reported as below.

Sample 6:

88% Biodegradation by biological oxygen demand (BOD), 72% biodegradationby CO2 evolution, 95% by dissolved organic carbon (DOC) removal

Conclusion: Readily biodegradable

Sample 1:

60% by BOD, 46% by CO2, and 97% by DOC

Conclusion: Readily biodegradable

Sample 3:

100% by BOD, 81% by CO2, and 100% by DOC

Conclusion: Readily biodegradable

While the invention has been described above according to its preferredembodiments, it can be modified within the spirit and scope of thisdisclosure. This application is therefore intended to cover anyvariations, uses, or adaptations of the invention using the generalprinciples disclosed herein. Further, the application is intended tocover such departures from the present disclosure as come within theknown or customary practice in the art to which this invention pertainsand which fall within the limits of the following claims.

What is claimed is:
 1. A process for preparing an aldehyde product or asulfonated surfactant product, comprising: (1) combining at least oneolefin and at least one coordination-insertion catalyst and, optionally,an alpha-olefin, wherein the coordination-insertion catalyst is ametal-ligand complex wherein the metal is selected from zirconium,hafnium and titanium, and has an ethylene/octene reactivity ratio up to20 at an operating reactor temperature, and a kinetic chain length up to20 monomer units; under conditions such that at least one oligomerproduct is formed, wherein the oligomer product includes a main carbonchain containing an average of between 0.5 and 2.5 branches, whereinmore than 50% of the branches are ethyl branches, wherein the branchesare located on average more than one carbon away from each end of themain carbon chain in more than 20% of oligomer product molecules,wherein the branches are situated at a second carbon relative to anunsaturated end of the main carbon chain in less than 40% of theoligomer product molecules, and wherein the oligomer product containsgreater than 50% vinyl olefin; (2) fractionating the oligomer product toproduce a fractionated oligomer product, such that the average carbonnumber of the fractionated oligomer product is between 8 and 28; (3)hydroformylating the fractionated oligomer product to produce analdehyde product or sulfonating the fractionated oligomer product toproduce a sulfonated surfactant product; and wherein thecoordination-insertion catalyst is selected from the group consistingof:

and combinations thereof.
 2. A process according to claim 1, wherein theat least one olefin is ethylene and an alpha-olefin is not used.
 3. Aprocess according to claim 1, wherein the at least one olefin is anolefin mixture.
 4. A process according to claim 3, wherein the olefinmixture includes olefins with vinyl groups, olefins with vinylidenegroups, and olefins with vinylene groups.
 5. A process according toclaim 1, further comprising use of a rhodium catalyst with anorganophosphorus ligand in the hydroformylating step (3).
 6. A processfor preparing an aldehyde product or a sulfonated surfactant product,comprising: (1) combining at least one olefin and at least onecoordination-insertion catalyst and, optionally, an alpha-olefin,wherein the coordination-insertion catalyst is a metal-ligand complexwherein the metal is selected from zirconium, hafnium and titanium, andhas an ethylene/octene reactivity ratio up to 20 at an operating reactortemperature, and a kinetic chain length up to 20 monomer units; underconditions such that at least one oligomer product is formed, whereinthe oligomer product includes a main carbon chain containing an averageof between 0.5 and 2.5 branches, wherein more than 50% of the branchesare ethyl branches, wherein the branches are located on average morethan one carbon away from each end of the main carbon chain in more than20% of oligomer product molecules, wherein the branches are situated ata second carbon relative to an unsaturated end of the main carbon chainin less than 40% of the oligomer product molecules, and wherein theoligomer product contains greater than 50% vinyl olefin; (2)fractionating the oligomer product to produce a fractionated oligomerproduct, such that the average carbon number of the fractionatedoligomer product is between 8 and 28; (3) hydroformylating thefractionated oligomer product to produce an aldehyde product orsulfonating the fractionated oligomer product to produce a sulfonatedsurfactant product; and wherein the metal-ligand complex is a compoundof the formula

 wherein M is the metal center, and is a Group 4 metal selected fromtitanium, zirconium or hafnium;  T is an optional bridging group which,if present, is selected from dialkylsilyl, dialkylmethyl, ethylenyl(—CH₂—CH₂—) or hydrocarbylethylenyl wherein one, two, three or four ofthe hydrogen atoms in ethylenyl are substituted by hydrocarbyl, wherehydrocarbyl can be independently C₁ to C₁₆ alkyl or phenyl, tolyl, orxylyl, and when T is present, the catalyst represented can be in aracemic or a meso form; L₁ and L₂ are the same or differentcyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl rings,optionally substituted, that are each bonded to M, or L₁ and L₂ are thesame or different cyclopentadienyl, indenyl, tetrahydroindenyl orfluorenyl, which are optionally substituted, in which any two adjacent Rgroups on these rings are optionally joined to form a substituted orunsubstituted, saturated, partially unsaturated, or aromatic cyclic orpolycyclic substituent; Z is nitrogen, oxygen or phosphorus; R′ is acyclic linear or branched C₁, C₄₀ alkyl or substituted alkyl group; andX₁ and X₂ are, independently, hydrogen, halogen, hydride radicals,hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbylradicals, substituted halocarbyl radicals, silylcarbyl radicals,substituted silylcarbyl radicals, germylcarbyl radicals, or substitutedgermylcarbyl radicals; or both X are joined and bound to the metal atomto form a metallacycle ring containing from 3 to 20 carbon atoms; orboth together can be an olefin, diolefin or aryne ligand.
 7. A processaccording to claim 6, wherein the at least one olefin is ethylene and analpha-olefin is not used.
 8. A process according to claim 6, wherein theat least one olefin is an olefin mixture.
 9. A process according toclaim 8, wherein the olefin mixture includes olefins with vinyl groups,olefins with vinylidene groups, and olefins with vinylene groups.
 10. Aprocess according to claim 6, further comprising use of a rhodiumcatalyst with an organophosphorus ligand in the hydroformylating step(3).